Cyclodextrins (CDs), cyclic oligosaccharides commonly composed of six, seven or eight (alpha, beta, and gamma respectively) D-glucopyranosyl units connected by alpha-(1,4)- glycosidic linkages, have the ability to form inclusion complexes with a wide range of substrates in aqueous solution. This property has led to their applications in different areas such as enzyme mimics, catalysis and the encapsulation. of drugs. ESI-MS has begun to be viewed as a useful tool for investigating the general area of molecular recognition thus providing a powerful mean for the analysis of a wide array of host-guest complexes and other non covalent complexes present in solution. The evaluation of the binding selectivity of beta-cyclodextrin towards the first group alkali cations is reported. The estimation of the affinity degrees has been achieved by competition ESI-MS experiments. In these experiments beta-CD was incubated at the presence of two different cations at the same time, and the ratio of the mass peaks corresponding to the two complexes was calculated. In general, it appears a much larger affinity of the beta-cyclodextrin molecule with sodium with respect to all the other alkaline cations, thus giving evidence that it is the size of the beta-cyclodextrin ring in relation with the cationic radius, which drives the formation of what, at this point, could be defined as an inclusion complex.